WO2017128969A1

WO2017128969A1 - System and method for producing 3.5-valent highly pure vanadium electrolyte

Info

Publication number: WO2017128969A1
Application number: PCT/CN2017/071207
Authority: WO
Inventors: 范川林; 朱庆山; 杨海涛; 牟文恒; 刘吉斌; 王存虎; 班琦勋
Original assignee: 中国科学院过程工程研究所; 北京中凯宏德科技有限公司
Priority date: 2016-01-28
Filing date: 2017-01-16
Publication date: 2017-08-03
Also published as: CA3012273A1; ZA201805714B; JP6588652B2; AU2017210930A1; EP3401991B1; AU2017210930B2; JP2019505073A; NZ744570A; CN106257728A; US10673088B2; US20190044173A1; CN106257728B; RU2695083C1; EP3401991A1; EP3401991A4

Abstract

A system and method for producing a 3.5-valent highly pure vanadium electrolyte: use a fluidized bed (2) to hydrolyze highly pure vanadium oxytrichloride to vanadium pentoxide by means of gas-phase hydrolysis, accurately control the reduction of vanadium pentoxide in a reducing fluidized bed (5) to a low-valent vanadium oxide with an average vanadium valence state at 3.5, and under an externally applied microwave field, add water and a sulfuric acid solution to dissolve at a low temperature to obtain a 3.5-valent highly pure vanadium electrolyte, which can be directly used in new piles of vanadium redox flow batteries. The preparation of vanadium pentoxide by means of gas-phase hydrolysis by using the fluidized bed (2) has a short flow and high efficiency. By providing an internal member within the reducing fluidized bed (5), the accurate regulation of the valence state of reduction products may be achieved. The special chemical effect of the microwave field promotes dissolution of vanadium oxides and activates vanadium ions. The dissolution and preparation of an electrolyte in a low temperature range greatly improves the activity of the electrolyte. The method has advantages of short flow, high efficiency, environmental friendliness, and steady product quality, which is applicable to large-scale industrial productions, while offering excellent economic and social benefits.

Description

System and method for producing 3.5-valent high-purity vanadium electrolyte

Technical field

The invention belongs to the field of energy and chemical industry, and particularly relates to a system and a method for producing a 3.5-valent high-purity vanadium electrolyte.

Background technique

Traditional fossil fuels have always been the main source of energy. Due to long-term exploitation and heavy use, they are facing the problem of depletion of resources and serious environmental pollution. The development and utilization of clean renewable energy such as wind, water, solar, and tidal energy has gradually attracted the attention of human society. However, renewable energy sources are inherently intermittent, and existing energy management systems are difficult to use effectively.

Energy storage technology is one of the ways to solve such problems. In a wide variety of energy storage systems, all-vanadium flow battery (VRB) is a compelling energy storage device. The biggest advantage of VRB is its flexibility – power and energy storage capacity are independent. The power of the VRB is determined by the number of battery cells and the effective electrode area of the battery cells, and the energy storage capacity is determined by the concentration of the active material in the electrolyte and the volume of the electrolyte. Each battery cell consists of two pole chambers (the positive and negative chambers) separated by a proton exchange membrane. An electrolyte solution, a vanadium sulfate solution, is used to store energy. When the electrolyte flows through the battery cells, V(IV)/V(V) and V(II)/V(III) redox reactions occur in the positive and negative chambers, respectively. Vanadium electrolyte is a vital component of all vanadium redox flow batteries.

Vanadium battery new reactor configuration generally uses V (III) and V (IV) concentration ratio of 1:1 mixed vanadium electrolyte, that is, the average valence state of vanadium ions in the electrolyte is 3.5. The electrolyte can be directly used in the positive and negative electrodes, and the operation is simple. The purity of the vanadium electrolyte plays a crucial role in battery performance. When the impurity concentration in the electrolyte is high, the following problems are caused: (1) The impurity ions and the vanadium ions have a competitive reaction, and the battery efficiency is lowered. (2) In the positive electrode chamber, impurity ions are deposited on the graphite felt electrode, blocking the voids of the graphite felt, reducing the specific surface area of the graphite felt, thereby affecting the charge and discharge efficiency. (3) In the negative electrode chamber, the impurity ions will catalyze the hydrogen over-potential, and the gas will affect the pressure balance inside the battery. (4) Impurity ions reduce the lifetime of the proton exchange membrane. (5) Impurity ions affect the stability of vanadium ions, leading to premature aging of the electrolyte.

There are several methods for preparing the VRB electrolyte: (1) VOSO ₄ method: US Pat. No. 849,094 discloses a method for preparing V(III) and V(IV) concentrations by electrochemically adjusting the valence state by dissolving VOSO ₄ in a sulfuric acid solution. A vanadium electrolyte mixed with a ratio of 1:1. The main problem of this method is that the VOSO ₄ manufacturing process is relatively complicated and expensive, which is not conducive to large-scale popularization and use in VRB; VOSO _{4 is} difficult to achieve high purification, and the electrolyte configured by this process contains more impurities; Electrochemical treatment to adjust the V(III) and V(IV) concentration ratio to 1:1, so that the average valence state of vanadium ions in the electrolyte is 3.5. (2) Chemical reduction method: Chinese patent CN101562256 discloses a method of adding a reducing agent such as oxalic acid or butyraldehyde to a mixed system of V ₂ O ₅ and a sulfuric acid solution, and maintaining it at 50-100 ° C for 0.5-10 hours to prepare by chemical reduction. A vanadium electrolyte in which V(III) and V(IV) are mixed. The main problem of this method is that the degree of reduction is not easy to control accurately; the V ₂ O ₅ prepared by the prior process is difficult to achieve high purification, and the electrolyte configured by this process contains more impurities; the addition of reducing agent introduces new impurities into the vanadium electrolysis. Liquid system, affecting the purity of the electrolyte. (3) Electrolysis method: International PCT patent AKU88/000471 introduces the addition of V ₂ O ₅ to sulfuric acid solution, and the preparation of mixed vanadium electrolyte with V(III) and V(IV) concentration ratio of 1:1 by constant current electrolysis. . Preparation of vanadium electrolyte by electrolysis is suitable for large-scale electrolyte production, but requires pre-activation treatment, requires additional electrolysis equipment and consumes electric energy; also has the problem of more electrolyte impurities (4) method of dissolving low-cost vanadium oxide : Chinese patent CN101728560A discloses the use of high purity V ₂ O ₃ as raw material, dissolved in 1:1 dilute sulfuric acid at a temperature of 80-150 ° C to prepare a V ₂ (SO ₄ ) ₃ solution for the negative electrode electrolyte. The main problem of this kind of process is that the V(III) vanadium ion hydrate easily forms an oxygen bridge to produce polycondensation at a temperature of 80-150 ° C, resulting in a decrease in electrolyte activity and a lack of activation step; this method can only be used for Preparation of negative electrode electrolyte, the application surface is narrow; the patented industrial high purity V ₂ O ₃ , the total vanadium content is 67%, equivalent to 98.5% purity, still contains many impurity ions. Chinese patent CN102468509A discloses a preparation method of a vanadium battery electrolyte, which uses V-ammonium vanadate and ammonium hydrogencarbonate as raw materials to prepare V ₂ O _{3 by} section calcination at 200-300 ° C and 600-700 ° C. The V ₂ O _{3 is} dissolved in dilute sulfuric acid at 50 to 120 ° C for 5 to 20 hours to obtain a V ₂ (SO ₄ ) ₃ solution. The V ₂ O _{5 was} dissolved in a V ₂ (SO ₄ ) ₃ solution at 80 to 110 ° C for 1 to 3 hours to obtain a vanadium battery electrolyte having an average vanadium ion concentration of 3.5. The V ₂ (SO ₄ ) ₃ solution was prepared in this patent for use in a negative electrode electrolyte. The main problem of this method is that the V(III) vanadium ion hydrate easily forms an oxygen bridge bond at a higher temperature to cause polycondensation, resulting in a decrease in electrolyte activity and a lack of activation step; the electrolyte purity is not high. Chinese patent CN103401010A discloses a preparation method of an all-vanadium redox flow battery electrolyte, which is prepared by reducing V ₂ O ₅ powder in hydrogen to prepare V ₂ O ₄ powder and V ₂ O ₃ powder. V ₂ O ₄ and V ₂ O ₃ were respectively dissolved in concentrated sulfuric acid to obtain a positive electrode and a negative electrode electrolyte of the vanadium battery. The main problem of this patent is that no specific reduction process is given, and V ₂ O ₅ powder is reduced in hydrogen to prepare V ₂ O ₄ powder, which is prone to over-reduction or under-reduction, which requires precise control. The measures for precise control reduction are not listed; the purity is low; Chinese patents CN101880059A and CN102557134A disclose a fluidized reduction furnace and a reduction method for producing high-purity vanadium trioxide, and the heat exchange internal components are added through the fluidized bed to realize Enhanced heat transfer; using cyclone preheating to improve energy efficiency and achieve efficient preparation of V ₂ O ₃ . The methods described in these two patents are only applicable to the preparation of V ₂ O ₃ and are not suitable for the preparation of low-valent vanadium oxides of other valence states because the system does not have the function of precisely controlling the reduction.

In summary, there is a need in the art for a solution to the preparation process and technical requirements of an all-vanadium redox flow battery electrolyte. To achieve a simplified preparation process, improve electrolyte purity, improve electrolyte configuration and ease of use.

Summary of the invention

In view of the above problems, the present invention proposes a system and method for producing a 3.5-valent high-purity vanadium electrolyte to simplify the preparation process, improve the purity of the electrolyte, and improve the simplicity of the electrolyte. In order to achieve these objectives, the present invention adopts the following technical solutions:

The invention provides a system for producing a 3.5-valent high-purity vanadium electrolyte, the system comprising a vanadium oxychloride storage tank, a gas phase hydrolysis fluidized bed 2, a vanadium pentoxide feeding device 3, a preheating dust removing device 4, a reducing fluidized bed 5, primary cooling device 6, secondary cooling device 7, low-cost vanadium oxide feeding device 8, dissolution activation device 9, exhaust gas extraction absorption tower 10, induced draft fan 11 and chimney 12;

The gas phase hydrolysis fluidized bed 2 comprises a vanadium oxychloride vaporizer 2-1, a clean water vaporizer 2-2, a chloride spray gun 2-3, a gas phase hydrolysis fluidized bed main body 2-4, a hydrolyzed fluidized bed discharger 2 -5, hydrochloric acid exhaust gas absorber 2-6;

The vanadium pentoxide feeding device 3 comprises a vanadium pentoxide silo 3-1 and a vanadium pentoxide screw feeder 3-2;

The preheating dust removing device 4 comprises a venturi preheater 4-1, a first cyclone separator 4-2, a cyclone preheater 4-3, a bag filter 4-4;

The reducing fluidized bed 5 comprises a feeder 5-1, a bed 5-2, a discharger 5-3, a gas heater 5-4, a gas purifier 5-5, a cyclone 5-6;

The primary cooling device 6 includes a venturi cooler 6-1, a second cyclone separator 6-2, a cyclone cooler 6-3;

The low-cost vanadium oxide feeding device 8 comprises a low-cost vanadium oxide silo 8-1 and a low-cost vanadium oxide screw feeder 8-2;

The dissolution activation device 9 comprises a stirring dissolution device 9-1 and a microwave activation device 9-2;

The outlet of the bottom of the vanadium oxychloride vapor storage tank 1 is connected to the inlet of the vanadium oxychloride vaporizer 2-1 through a pipeline; the inlet of the vanadium oxychloride vaporizer 2-1 is connected to the purified nitrogen manifold through a pipeline The gas outlet of the vanadium oxychloride vaporizer 2-1 is connected to the inlet of the chloride spray gun 2-3 through a pipe; the inlet of the clean water vaporizer 2-2 is separately purified from the clean water main pipe through the pipeline The air main pipe is connected; the air outlet of the clean water vaporizer 2-2 is connected to the air inlet of the bottom of the gas phase hydrolysis fluidized bed main body 2-4 through a pipe; the gas phase hydrolysis fluidized bed main body 2-4 is enlarged The gas outlet at the top is connected to the gas inlet of the hydrochloric acid exhaust gas absorber 2-6 through a pipe; the hydrochloric acid tail gas absorber 2-6 is provided with a hydrochloric acid solution outlet; the hydrochloric acid exhaust gas absorber 2-6 gas outlet Connected to the gas inlet of the exhaust gas eluting absorber 10 through a pipe; the gas phase hydrolyzed fluidized bed main The discharge port at the upper portion of the body 2-4 is connected to the feed port of the hydrolyzed fluidized bed discharger 2-5 through a pipe; the loose air inlet port of the hydrolyzed fluidized bed discharger 2-5 passes through the pipe Connected to the purified nitrogen manifold; the discharge port of the hydrolyzed fluidized bed discharger 2-5 is connected to the inlet of the vanadium pentoxide bin 3-1 through a pipe;

The outlet of the bottom of the vanadium pentoxide silo 3-1 is connected to the inlet of the vanadium pentoxide screw feeder 3-2; the outlet of the vanadium pentoxide screw feeder 3-2 a port and a feed port of the venturi preheater 4-1 connected by a pipe;

The discharge port of the venturi preheater 4-1 is connected to the feed port of the first cyclone separator 4-2 through a pipe, and the air outlet of the first cyclone separator 4-2 and the bag The air inlet of the dust collector 4-4 is connected by a pipe; the discharge port of the first cyclone 4-2 is connected to the air inlet of the cyclone preheater 4-3 through a pipe; the bag filter The air outlet of 4-4 is connected to the air inlet of the exhaust gas absorbing absorber 10 through a pipe; the fine powder outlet of the bag filter 4-4 and the air inlet of the cyclone preheater 4-3 are passed through; a gas pipe connecting the gas inlet of the cyclone preheater 4-3 to the gas outlet of the cyclone dust collector 5-6; the gas outlet of the cyclone preheater 4-3 and the venturi pre The air inlet of the heat exchanger 4-1 is connected by a pipe; the discharge port of the cyclone preheater 4-3 is connected to the feed port of the feeder 5-1 through a pipe;

The discharge port of the feeder 5-1 is connected to the inlet of the bed 5-2 through a pipe; the loose air inlet of the feeder 5-1 is connected to the purified nitrogen main pipe; the bed body The air inlet of 5-2 is connected to the air outlet of the gas heater 5-4 through a pipe; the vertical baffle is arranged in the bed 5-2; the discharge port of the bed 5-2 and the row The inlet of the feeder 5-3 is connected by a pipe; the outlet of the bed 5-2 is connected to the inlet of the cyclone 5-6 through a pipe; the outlet of the cyclone 5-6 a gas port is connected to the inlet of the cyclone preheater 4-3 through a pipe; a discharge port of the cyclone 5-6 is connected to a feed port of the discharger 5-3 through a pipe; The discharge port of the discharger 5-3 is connected to the inlet of the venturi cooler 6-1 through a pipe; the loose air inlet of the discharger 5-3 is connected to the purge nitrogen main pipe; the gas heating The air outlet of the device 5-4 is connected to the air inlet of the bed 5-2 through a pipe; the air inlet of the gas heater 5-4 is respectively connected to the air outlet of the gas purifier 5-5 The air outlet of the second cyclone separator 6-2 passes The fuel inlet of the gas heater 5-4 is connected to the fuel main pipe through a pipe; the combustion air inlet of the gas heater 5-4 is connected to the compressed air main pipe through a pipe; the gas purifier 5-5 The air inlet and the reducing gas manifold are connected by a pipe;

a feed port of the venturi cooler 6-1 is connected to a discharge port of the discharger 5-3; an intake port of the venturi cooler 6-1 and the cyclone cooler 6-3 The air outlets are connected by pipes; the venturi cooler 6-1 The air outlet is connected to the air inlet of the second cyclone separator 6-2 through a pipe; the air outlet of the second cyclone separator 6-2 and the air inlet of the gas heater 5-4 pass through the pipeline Connected; the discharge port of the second cyclone separator 6-2 is connected to the air inlet of the cyclone cooler 6-3; the air inlet of the cyclone cooler 6-3 is connected to the purified nitrogen manifold; An air outlet of the cyclone cooler 6-3 is connected to an air inlet of the venturi cooler 6-1 through a pipe; a discharge port of the cyclone cooler 6-3 and the secondary cooling device 7 The material port is connected by a pipe;

The feed port of the secondary cooling device 7 is connected to the discharge port of the cyclone cooler 6-3 through a pipe; the discharge port of the secondary cooling device 7 and the low-cost vanadium oxide silo 8- The feed port of the first cooling device 7 is connected to the process water main pipe through a pipe; the water outlet of the secondary cooling device 7 is connected to the water inlet of the water cooling system through a pipe;

The discharge port at the bottom of the low-priced vanadium oxide silo 8-1 is connected to the feed port of the low-cost vanadium oxide screw feeder 8-2; the low-cost vanadium oxide screw feeder 8-2 a discharge port and a feed port of the dissolution activation device 9 are connected through a pipe;

The clean water inlet of the stirring and dissolving device 9-1 is connected to the clean water main pipe through a pipe; the sulfuric acid solution inlet of the stirring and dissolving device 9-1 is connected to the sulfuric acid solution main pipe through a pipe; and the gas of the stirring and dissolving device 9-1 is stirred. The outlet is connected to the inlet of the exhaust gas absorbing absorption tower 10 through a pipe; the stirring and dissolving device 9-1 is placed inside the microwave activating device 9-2;

The gas outlet of the exhaust gas leaching absorption tower 10 is connected to the gas inlet of the induced draft fan 11 through a pipe; the gas outlet of the induced draft fan 11 is connected to the gas inlet at the bottom of the chimney 12 through a pipe.

The method for producing a 3.5-valent high-purity vanadium electrolyte based on the above system of the present invention comprises the following steps:

The vanadium oxychloride in the vanadium pentoxide storage tank 1 and the nitrogen from the purified nitrogen main pipe are preheated by the vaporization of the vanadium oxychloride vaporizer 2-1, and then enter the gas phase through the chloride spray gun 2-3. Hydrolyzing the fluidized bed main body 2-4; the clean water and the purified air are vaporized and preheated by the clean water vaporizer 2-2, and then sent to the gas phase hydrolysis fluidized bed main body 2-4 to cause hydrolysis of vanadium oxychloride. And maintaining the fluidization of the powder material to form vanadium pentoxide powder and hydrogen chloride-rich hydrolyzed flue gas; the vanadium pentoxide powder is discharged through the hydrolyzed fluidized bed discharger 2-5 In the vanadium pentoxide silo 3-1; the hydrolyzed flue gas is removed by the enlarged section of the gas phase hydrolysis fluidized bed main body 2-4, and then enters the hydrochloric acid exhaust gas absorber 2-6 for absorption treatment to form a hydrochloric acid solution. By-product, absorbing exhaust gas into the exhaust gas leaching absorber 10 for processing;

The vanadium pentoxide in the vanadium pentoxide silo 3-1 sequentially enters the vanadium pentoxide screw feeder 3-2. After the venturi preheater 4-1, the first cyclone separator 4-2, the cyclone preheater 4-3, and the fine powder recovered from the bag filter (4-4) The particles enter the bed 5-2 together through the feeder 5-1; the purified nitrogen passes through the cyclone cooler 6-3, the venturi cooler 6-1, the second After the cyclone separator 6-2 is preheated, it is mixed with the purified reducing gas from the gas purifier 5-5, and then preheated by the gas heater 5-4 to enter the bed 5-2 to be pentridized. The vanadium powder material maintains fluidization and reduces it to obtain a low-valent vanadium oxide powder and a reduced flue gas; the low-valent vanadium oxide passes through the discharge port of the bed 5-2 and the cyclone The fine powder recovered by the dust remover 5-6 sequentially enters the discharger 5-3, the venturi cooler 6-1, the second cyclone separator 6-2, and the cyclone cooler 6-3. After the secondary cooler 7 is cooled, it enters the low-cost vanadium oxide silo 8-1; the reduced flue gas in the bed 5-2 sequentially enters the cyclone 5-6, Cyclone preheater 4-3, the venturi preheater 4 -1, the first cyclone separator 4-2, after being dedusted by the bag filter 4-4, enters the exhaust gas eluting absorber 10, and the gas discharged after being absorbed by the alkali solution is passed through the induced draft fan 11 After being sent into the chimney 12, it is emptied;

The low-valent vanadium oxide in the low-valent vanadium oxide silo 8-1 enters the stirring and dissolving device 9-1 through the low-valent vanadium oxide screw feeder 8-2, in the microwave activating device 9 -2 provides a microwave field, and dissolves with a sulfuric acid solution from the clean water and sulfuric acid solution main pipe of the clean water main pipe to obtain a high-purity vanadium electrolyte, and the generated acid mist gas is sent to the exhaust gas elution absorber. 10 for processing.

One of the features of the present invention is that the vanadium oxychloride raw material has a purity of 99% to 99.9999%, that is, 2N to 6N.

The second feature of the present invention is that in the vanadium oxychloride vaporizer 2-1, the vaporization operation temperature is 40 to 600 ° C, and the molar ratio of nitrogen gas to vanadium oxychloride is 0.10 to 10.00.

The third feature of the present invention is that in the clean water vaporizer 2-2, the vaporization operation temperature is 40 to 600 ° C, and the mass ratio of air to water is 0.10 to 10.00.

The fourth feature of the present invention is that in the gas phase hydrolysis fluidized bed main body 2-4, the vanadium pentoxide powder is directly prepared by vapor phase hydrolysis of vanadium oxychloride, and the vapor phase hydrolysis process is carried out by introducing water vapor and vanadium oxychloride. The mass ratio is 0.10 to 10.00, the gas phase hydrolysis operation temperature is 100 to 600 ° C, and the average residence time of the powder is 15 to 300 min.

The fifth feature of the present invention is that in the reduced fluidized bed main body 5-2, the operating temperature of the reduction is 400 to 700 ° C, and the reducing gas is purified by the purifier 5-5, and the organic matter content is less than 1 mg/Nm ³ . The total content of solid particles is less than 2 mg/Nm ³ , and the integral number of reducing gas in the mixed gas of nitrogen and reducing gas is 10% to 90%, and the average residence time of the powder is 30 to 90 minutes.

A sixth feature of the present invention resides in that the sulfuric acid solution is a sulfuric acid solution having an electronic grade purity of 4.0 to 10.0 mol/L.

A seventh feature of the present invention is that the high purity vanadium electrolyte is a vanadium electrolyte having a molar ratio of V(III) and V(IV) vanadium ions of 1:1, and the average valence state of the vanadium ions is 3.5. The obtained 3.5-valent high-purity vanadium electrolyte can be directly used in a new stack of all-vanadium redox flow batteries.

The eighth feature of the present invention is that in the dissolution activation device 9, the external microwave field is used to assist the dissolution and activation of the vanadium ion of the low-valent vanadium oxide, the dissolution activation time is 30 to 300 minutes, and the dissolution activation temperature is 20 to 45 ° C, microwave power density is 10 ~ 300W / L, microwave frequency is 2450MHz or 916MHz,

The electrolyte produced by the invention has high purity, high activity, convenient electrolyte configuration and convenient use, and the invention has the following outstanding advantages over the prior art:

(1) High purity: High purity vanadium oxychloride having a purity of 2N to 6N is easily obtained by using vanadium oxychloride which is easily purified. Taking 5N vanadium oxychloride as an example, the present invention can prepare a low-cost vanadium oxide having a purity of 4N5 (that is, a purity of 99.995%), thereby preparing a high-purity vanadium electrolyte, in addition to the effective component, the total impurity content is less than 5 ppm;

(2) Fluidized gas phase hydrolysis: short process, large output, easy to industrial use;

(3) Precise control and reduction: the form of rectangular multi-cylinder fluidized bed is adopted to realize precise control and reduction of valence state;

(4) Realizing the sensible heat utilization of the high-temperature tail gas and the high-temperature reduction product in the fluidized bed: the high-temperature tail gas discharged from the reduced fluidized bed is directly contacted with the cold vanadium-containing material, and the cold-containing vanadium-containing material is heated while recovering the sensible heat of the high-temperature reducing tail gas; The reduction is directly contacted with the discharged high-temperature and low-valent vanadium oxide product by the purified nitrogen gas, and the purified nitrogen product is preheated while recovering the sensible heat of the high-temperature reduction product;

(5) Realizing the ultrafine powder open circuit: the reducing fluidized bed exhaust gas passes through the external cyclone separator, and the recovered powder enters the reducing fluidized bed discharger, realizing the open circuit of the fine powder particles and avoiding the closed circulation of the fine powder particles. ;

(6) High activity: promote the dissolution of vanadium oxide and activate vanadium ions through the special chemical effect of the microwave field, dissolve the electrolyte solution in the low temperature range (20-45 ° C), and greatly improve the electrolyte activity;

(7) Convenient transportation: The process of producing electrolyte in this process is short, suitable for on-site configuration of vanadium batteries, and can transport low-cost vanadium oxide, greatly reducing transportation costs;

(8) 3.5-valent electrolyte: It is suitable for the new stack configuration of vanadium battery. It can be directly used in the positive and negative chambers for easy operation.

The invention has low production energy consumption and operation cost, high product purity, stable quality, electrolyte configuration and assembly The advantages of clean and so on are suitable for large-scale industrial production of all vanadium redox flow battery electrolyte, and have good economic and social benefits.

DRAWINGS

The drawings are intended to provide a further explanation of the invention and are intended to be a part of the description of the invention.

Figure 1 is a schematic view showing the configuration of a 3.5-valent high-purity electrolyte system of the present invention.

Reference mark:

1. A vanadium oxychloride vanadium storage tank;

2. a gas phase hydrolysis fluidized bed;

2-1, vanadium oxychloride vaporizer; 2-2, clean water vaporizer; 2-3, chloride spray gun;

2-4, gas phase hydrolysis fluidized bed main body; 2-5, hydrolyzed fluidized bed discharger; 2-6, hydrochloric acid tail gas absorber;

3. Vanadium pentoxide feeding device;

3-1, vanadium pentoxide silo; 3-2, vanadium pentoxide spiral feeder;

4. Preheating dust removal device;

4-1, Venturi preheater; 4-2, first cyclone separator; 4-3, cyclone preheater; 4-4, bag filter;

5. Reducing the fluidized bed;

5-1, feeder; 5-2, bed body; 5-3, discharge device;

5-4, gas heater; 5-5, gas purifier; 5-6, cyclone dust collector;

6. Primary cooling device;

6-1, Venturi cooler; 6-2, second cyclone separator; 6-3, cyclone cooler;

8. Low-cost vanadium oxide feeding device;

8-1, low-cost vanadium oxide silo; 8-2, low-cost vanadium oxide screw feeder;

9. Dissolution activation device;

9-1, stirring and dissolving device; 9-2, microwave activating device;

10. Exhaust gas absorbing absorption tower;

11, induced draft fan;

12. Chimney.

detailed description

The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings of the present invention. It is apparent that the described embodiments are part of the embodiments of the invention, and not all of the embodiments. It should be noted that the embodiments are only used to illustrate the technical solutions of the present invention, and are not limited thereto.

Example 1

Referring to Figure 1, the system for producing a 3.5-valent high-purity vanadium electrolyte used in the present embodiment includes a vanadium oxychloride vanadium 1, a gas phase hydrolyzed fluidized bed 2, a vanadium pentoxide feeding device 3, and a preheating dust removing device 4. , reducing fluidized bed 5, primary cooling device 6, secondary cooling device 7, low-cost vanadium oxide feeding device 8, dissolution activation device 9, exhaust gas elution absorption tower 10, induced draft fan 11 and chimney 12;

The outlet of the bottom of the vanadium oxychloride vapor storage tank 1 is connected to the inlet of the vanadium oxychloride vaporizer 2-1 through a pipeline; the inlet of the vanadium oxychloride vaporizer 2-1 is connected to the purified nitrogen manifold through a pipeline The gas outlet of the vanadium oxychloride vaporizer 2-1 is connected to the inlet of the chloride spray gun 2-3 through a pipe; the inlet of the clean water vaporizer 2-2 is separately purified from the clean water main pipe through the pipeline The air main pipe is connected; the air outlet of the clean water vaporizer 2-2 is connected to the air inlet of the bottom of the gas phase hydrolysis fluidized bed main body 2-4 through a pipe; the gas phase hydrolysis fluidized bed main body 2-4 is enlarged The gas outlet at the top is connected to the gas inlet of the hydrochloric acid exhaust gas absorber 2-6 through a pipe a hydrochloric acid solution outlet is disposed at the bottom of the hydrochloric acid exhaust gas absorber 2-6; a gas outlet of the hydrochloric acid exhaust gas absorber 2-6 is connected to a gas inlet of the exhaust gas eluting absorber 10 through a pipe; The discharge port at the upper part of the hydrolyzed fluidized bed main body 2-4 is connected to the feed port of the hydrolyzed fluidized bed discharger 2-5 through a pipe; the loose wind of the hydrolyzed fluidized bed discharger 2-5 The gas inlet is connected to the purified nitrogen manifold through a pipeline; the discharge port of the hydrolysis fluidized bed discharger 2-5 is connected to the inlet of the vanadium pentoxide silo 3-1 through a pipeline;

a feed port of the venturi cooler 6-1 is connected to a discharge port of the discharger 5-3; an intake port of the venturi cooler 6-1 and the cyclone cooler 6-3 The air outlet is connected by a pipe; the air outlet of the venturi cooler 6-1 is connected to the air inlet of the second cyclone 6-2 through a pipe; the second cyclone 6-2 is discharged a gas port is connected to the gas inlet of the gas heater 5-4 through a pipe; a discharge port of the second cyclone separator 6-2 is connected to an air inlet of the cyclone cooler 6-3; the cyclone The air inlet of the cooler 6-3 is connected to the purified nitrogen manifold; the air outlet of the cyclone cooler 6-3 is connected to the air inlet of the venturi cooler 6-1 through a pipe; the cyclone cooler 6 a discharge port of -3 is connected to a feed port of the secondary cooling device 7 through a pipe;

Example 2

This embodiment uses the above system to produce a 3.5-valent high-purity vanadium electrolyte, and the specific method includes the following steps: vanadium oxychloride in the vanadium oxychloride tank 1 and nitrogen from the nitrogen-purifying manifold pass through the trichloroox The vanadium vaporizer 2-1 is vaporized and preheated, and then enters the gas phase hydrolysis fluidized bed main body 2-4 through the chloride spray gun 2-3; the clean water and the purified air are vaporized and preheated by the clean water vaporizer 2-2. Into the gas phase hydrolysis fluidized bed main body 2-4, the vanadium oxychloride is hydrolyzed, and the fluidization of the powder material is maintained to form vanadium pentoxide powder and hydrogen chloride-rich hydrolyzed flue gas; The divana powder is discharged into the vanadium pentoxide bin 3-1 through the hydrolyzed fluidized bed discharger 2-5; the hydrolyzed flue gas is expanded by the gas phase hydrolysis fluidized bed main body 2-4 After the dust is removed from the section, the tail gas is sucked into the hydrochloric acid. The receiver 2-6 performs an absorption treatment to form a by-product of the hydrochloric acid solution, and absorbs the exhaust gas into the exhaust gas leaching absorber 10 for treatment;

The vanadium pentoxide in the vanadium pentoxide silo 3-1 sequentially enters the vanadium pentoxide screw feeder 3-2, the venturi preheater 4-1, the first cyclone separator 4-2. After the cyclone preheater 4-3, together with the fine powder particles recovered from the bag filter (4-4), enter the bed body through the feeder 5-1. 2; the purified nitrogen gas is sequentially preheated by the cyclone cooler 6-3, the venturi cooler 6-1, the second cyclone separator 6-2, and from the gas purifier 5- The purified reducing gas mixture of 5 is preheated by the gas heater 5-4 and then enters the bed 5-2 to maintain the fluidization of the vanadium pentoxide powder material and reduce it, resulting in low a vanadium oxide powder and a reducing flue gas; the low-valent vanadium oxide sequentially enters the discharger 5 through the discharge port of the bed 5-2 and the fine powder recovered by the cyclone 5-6. -3, the venturi cooler 6-1, the second cyclone separator 6-2, the cyclone cooler 6-3, the secondary cooler 7 are cooled, and then enter the low-valent vanadium oxidation In the material silo 8-1; in the bed 5-2 The reducing flue gas sequentially enters the cyclone 5-6, the cyclone preheater 4-3, the venturi preheater 4-1, the first cyclone separator 4-2, and the bag After the dust remover 4-4 is dusted, the exhaust gas leaching absorber 10 is introduced, and the gas discharged after being absorbed by the alkali solution is sent to the chimney 12 through the induced draft fan 11 and then emptied;

Example 3

In this embodiment, vanadium oxychloride (purity of 2N or more) is used as a raw material, and the treatment amount is 3 kg/h. In the vanadium oxychloride vaporizer 2-1, the vaporization operation temperature is 40 ° C, and the molar ratio of nitrogen to vanadium oxychloride is 10:1; in the clean water vaporizer 2-2, the vaporization operation temperature is 40 ° C, the air to water mass ratio is 10:1; in the gas phase hydrolysis fluidized bed body 2-4, the vapor phase hydrolysis process passes into the water vapor and The mass ratio of vanadium oxychloride to 10:1, the gas phase hydrolysis operation temperature is 100 ° C, the average residence time of the powder material is 300 min; vanadium pentoxide is obtained; in the reduction fluidized bed 5, the bed 5-2 is introduced. The reducing gas is hydrogen, and the volume fraction of hydrogen in the mixed gas of nitrogen and hydrogen in the bed 5-2 is 10%, the average residence time of the powder is 90 min, and the operating temperature of the reducing fluidized bed is 400 ° C; a low-valent vanadium oxide having a valence of 3.5 and a purity of 98.5%; adding a sulfuric acid solution to the stirring and dissolving device 9-1 under microwave field conditions (4.0mol/L) and clean water (resistance 15.0MΩ·cm), operating temperature is 20°C, microwave power density is 10W/L, microwave frequency is 916MHz, and the average valence state of vanadium ions is 3.5 after activation for 300 minutes. Pure vanadium electrolyte, in addition to the effective components, the total content of impurities is less than 0.5%.

Example 4

In this embodiment, vanadium oxychloride (purity of 3N or more) is used as a raw material, and the treatment amount is 30 kg/h. In the vanadium oxychloride vaporizer 2-1, the vaporization operation temperature is 600 ° C, and the molar ratio of nitrogen to vanadium oxychloride is 1:10; in the clean water vaporizer 2-2, the vaporization operation temperature is 600 ° C, the air to water mass ratio is 1:10; in the gas phase hydrolysis fluidized bed main body 2-4, the vapor phase hydrolysis process is introduced into the water vapor and The mass ratio of vanadium oxychloride to 1:10, the gas phase hydrolysis operation temperature is 600 ° C, the average residence time of the powder material is 15 min, to obtain vanadium pentoxide; in the reduction fluidized bed 5, the bed 5-2 is introduced. The reducing gas is gas, the gas volume fraction of gas and nitrogen is 90%, the average residence time of the powder is 30 min, the operating temperature of the reducing fluidized bed is 700 ° C, the average valence of vanadium is 3.5, and the purity is 99.5. % of low-valent vanadium oxide; under microwave field conditions, adding sulfuric acid solution (10.0 mol/L) and clean water (resistivity 18.0 MΩ·cm) to the stirring and dissolving device 9-1, operating temperature is 45 ° C, microwave The power density is 300W/L, the microwave frequency is 2450MHz, and after 30 minutes of activation, the average valence state of vanadium ions is obtained. 3.5 vanadium electrolyte solution of high purity, in addition to the effective component, the total content is less than 0.05% of impurities.

Example 5

In this embodiment, vanadium oxychloride (purity of 4N or more) is used as a raw material, and the treatment amount is 300 kg/h. In the vanadium oxychloride vaporizer 2-1, the vaporization operation temperature is 200 ° C, and the molar ratio of nitrogen to vanadium oxychloride is 1:5; in the clean water vaporizer 2-2, the vaporization operation temperature is 200 ° C, the air to water mass ratio is 1:5; in the gas phase hydrolysis fluidized bed main body 2-4, the vapor phase hydrolysis process passes into the water vapor and The mass ratio of vanadium oxychloride to 1:5, the gas phase hydrolysis operation temperature is 200 ° C, the average residence time of the powder material is 120 min, to obtain vanadium pentoxide; in the reduction fluidized bed 5, the bed 5-2 is introduced. The reducing gas is gas, the gas volume fraction of gas and nitrogen is 80%, the average residence time of the powder is 45 min, the operating temperature of the reducing fluidized bed is 600 ° C, the average valence of vanadium is 3.5, and the purity is 99.95. % of low-valent vanadium oxide; under microwave field conditions, adding sulfuric acid solution (8.0 mol/L) and clean water (resistance 18.0 MΩ·cm) to the stirring and dissolving device 9-1, operating temperature is 40 ° C, microwave power The density is 200W/L, the microwave frequency is 2450MHz, and after 180 minutes of activation, the average valence state of vanadium ions is obtained. High purity vanadium electrolytic solution, in addition to the effective component, the total content of impurities is less than 0.005%, can be used directly in the vanadium battery new stack configuration.

Example 6

In this embodiment, vanadium oxychloride (purity of 5N or more) is used as a raw material, and the treatment amount is 3000 kg/h. In the vanadium oxychloride vaporizer 2-1, the vaporization operation temperature is 200 ° C, and the molar ratio of nitrogen to vanadium oxychloride is 1:1; in the clean water vaporizer 2-2, the vaporization operation temperature is 200 ° C, the air to water mass ratio is 1:1; in the gas phase hydrolysis fluidized bed body 2-4, the vapor phase hydrolysis process passes into the water vapor and The mass ratio of vanadium oxychloride to 1:1, the gas phase hydrolysis operation temperature is 200 ° C, the average residence time of the powder material is 60 min, to obtain vanadium pentoxide; in the reduction fluidized bed 5, the bed 5-2 is introduced. The reducing gas is hydrogen, the gas volume fraction of the mixed gas of hydrogen and nitrogen is 50%, the average residence time of the powder is 60 min, the operating temperature of the reducing fluidized bed is 500 ° C, the average valence state of vanadium is 3.5, and the purity is 4N5. (ie, purity 99.995%) of low-valent vanadium oxide; under microwave field conditions, adding sulfuric acid solution (6.0mol/L) and clean water (resistance 18.0MΩ·cm) to the stirring and dissolving device 9-1, the operating temperature is At 30 ° C, the microwave power density is 100 W / L, the microwave frequency is 916 MHz, after activation for 120 minutes, the vanadium ion is obtained. The high-purity vanadium electrolyte with a mean valence of 3.5, in addition to the effective components, has a total impurity content of less than 5 ppm and can be directly used in the new stack configuration of the vanadium battery.

Example 7

In this embodiment, the vanadium oxychloride (purity of 6N or more) is used as a raw material, and the treatment amount is 3000 kg/h. In the vanadium oxychloride vaporizer 2-1, the vaporization operation temperature is 200 ° C, and the molar ratio of nitrogen to vanadium oxychloride is 1:1; in the clean water vaporizer 2-2, the vaporization operation temperature is 200 ° C, the air to water mass ratio is 1:1; in the gas phase hydrolysis fluidized bed body 2-4, the vapor phase hydrolysis process passes into the water vapor and The mass ratio of vanadium oxychloride to 1:1, the gas phase hydrolysis operation temperature is 200 ° C, the average residence time of the powder material is 60 min, to obtain vanadium pentoxide; in the reduction fluidized bed 5, the bed 5-2 is introduced. The reducing gas is hydrogen, the gas volume fraction of the mixed gas of hydrogen and nitrogen is 50%, the average residence time of the powder is 60 min, the operating temperature of the reducing fluidized bed is 500 ° C, the average valence of vanadium is 3.5, and the purity is 5N5. (ie purity 99.9995%) of low-valent vanadium oxide; under microwave field conditions, adding sulfuric acid solution (6.0mol/L) and clean water (resistance 18.0MΩ·cm) to the stirring and dissolving device 9-1, the operating temperature is At 30 ° C, the microwave power density is 100 W / L, the microwave frequency is 916 MHz, after activation for 120 minutes, vanadium ions are obtained. 3.5 Median state of high purity vanadium electrolytic solution, in addition to the effective component is less than 1 ppm or the total content of impurities, can be used directly in the vanadium battery new stack configuration.

The invention has not been described in detail in the prior art and is well known in the art.

The invention may, of course, be embodied in various embodiments and various modifications and changes can be made by those skilled in the art without departing from the spirit and scope of the invention. Changes and modifications are intended to be included within the scope of the appended claims.

Claims

A system for producing a 3.5-valent high-purity vanadium electrolyte, characterized in that the system comprises a vanadium oxychloride vanadium storage tank (1), a gas phase hydrolysis fluidized bed (2), a vanadium pentoxide feeding device (3), Preheating dust removal device (4), reduction fluidized bed (5), primary cooling device (6), secondary cooling device (7), low-cost vanadium oxide feeding device (8), dissolution activation device (9), Exhaust gas absorbing absorption tower (10), induced draft fan (11) and chimney (12);

The gas phase hydrolysis fluidized bed (2) comprises a vanadium oxychloride vaporizer (2-1), a clean water vaporizer (2-2), a chloride spray gun (2-3), a gas phase hydrolysis fluidized bed main body (2-4) ), a hydrolyzed fluidized bed discharger (2-5), a hydrochloric acid tail gas absorber (2-6);

The vanadium pentoxide feeding device (3) comprises a vanadium pentoxide silo (3-1) and a vanadium pentoxide screw feeder (3-2);

The preheating dust removing device (4) comprises a venturi preheater (4-1), a first cyclone separator (4-2), a cyclone preheater (4-3), and a bag filter (4-4). ;

The reducing fluidized bed (5) comprises a feeder (5-1), a bed (5-2), a discharger (5-3), a gas heater (5-4), a gas purifier (5) -5), cyclone dust collector (5-6);

The primary cooling device (6) comprises a venturi cooler (6-1), a second cyclone separator (6-2), a cyclone cooler (6-3);

The low-cost vanadium oxide feeding device (8) comprises a low-cost vanadium oxide silo (8-1) and a low-cost vanadium oxide screw feeder (8-2);

The dissolution activation device (9) comprises a stirring dissolution device (9-1) and a microwave activation device (9-2);

The outlet of the bottom of the vanadium oxychloride tank (1) is connected to the inlet of the vanadium oxychloride vaporizer (2-1) through a pipe; the inlet of the vanadium oxychloride vaporizer (2-1) is passed The pipeline is connected to the purge nitrogen manifold; the gas outlet of the vanadium oxychloride vaporizer (2-1) is connected to the inlet of the chloride spray gun (2-3) through a pipe; the clean water vaporizer (2-2) The inlet of each of the inlets is connected to the clean water main pipe and the clean air main pipe through a pipe; the gas outlet of the clean water vaporizer (2-2) passes through the pipe and the gas inlet of the bottom portion of the gas phase hydrolysis fluidized bed main body (2-4) Connected; the gas outlet at the top of the enlarged section of the vapor-phase hydrolyzed fluidized bed body (2-4) is connected to the gas inlet of the hydrochloric acid exhaust gas absorber (2-6) through a pipe; the hydrochloric acid exhaust gas absorber (2) -6) a hydrochloric acid solution outlet is disposed at the bottom; a gas outlet of the hydrochloric acid exhaust gas absorber (2-6) is connected to a gas inlet of the exhaust gas eluting absorber (10) through a pipe; the gas phase hydrolyzed fluidized bed The discharge port at the upper part of the main body (2-4) passes through the pipe and the water The feed ports of the de-fluidized bed discharger (2-5) are connected; the loose air inlet of the hydrolyzed fluidized bed discharger (2-5) is connected to the purified nitrogen main pipe through a pipe; the hydrolysis flow The discharge opening of the chemical bed discharger (2-5) is connected to the inlet of the vanadium pentoxide silo (3-1) through a pipe;

a discharge port at the bottom of the vanadium pentoxide silo (3-1) is connected to a feed port of the vanadium pentoxide screw feeder (3-2); the vanadium pentoxide screw feeder ( The discharge port of 3-2) and the feed port of the venturi preheater (4-1) are connected by a pipe;

a discharge port of the venturi preheater (4-1) is connected to a feed port of the first cyclone separator (4-2) through a pipe, and the first cyclone separator (4-2) An air outlet is connected to the air inlet of the bag filter (4-4) through a pipe; a discharge port of the first cyclone (4-2) and the cyclone preheater (4-3) The air inlet is connected by a pipe; the air outlet of the bag filter (4-4) is connected to the air inlet of the exhaust gas absorbing absorber (10) through a pipe; the bag filter (4-4) a fine powder outlet is connected to an inlet of the cyclone preheater (4-3) through a pipe; an inlet of the cyclone preheater (4-3) and the cyclone (5-6) The air outlet is connected by a pipe; the air outlet of the cyclone preheater (4-3) is connected to the air inlet of the venturi preheater (4-1) through a pipe; the cyclone preheater (4- The discharge port of 3) is connected to the feed port of the feeder (5-1) through a pipe;

The discharge port of the feeder (5-1) is connected to the feed port of the bed body (5-2) through a pipe; the loose air inlet of the feeder (5-1) and the purge nitrogen gas pipe Connected; the air inlet of the bed body (5-2) is connected to the air outlet of the gas heater (5-4) through a pipe; the bed body (5-2) is provided with a vertical baffle; the bed The discharge port of the body (5-2) is connected to the feed port of the discharger (5-3) through a pipe; the air outlet of the bed body (5-2) and the cyclone dust collector (5- 6) The air inlet is connected by a pipe; the air outlet of the cyclone (5-6) is connected to the air inlet of the cyclone preheater (4-3) through a pipe; the cyclone (5) The discharge port of -6) is connected to the feed port of the discharger (5-3) through a pipe; the discharge port of the discharger (5-3) and the venturi cooler (6- The feed port of 1) is connected by a pipe; the loose air inlet of the discharger (5-3) is connected to the purge nitrogen main pipe; the gas outlet of the gas heater (5-4) and the bed body (5) -2) the air inlet is connected by a pipe; the air inlet of the gas heater (5-4) and the air outlet of the gas purifier (5-5) and the The gas outlet of the two cyclone separator (6-2) is connected by a pipe; the fuel inlet of the gas heater (5-4) is connected to the fuel main pipe through a pipe; the combustion air inlet of the gas heater (5-4) Connected to the compressed air manifold through a pipeline; the inlet of the gas purifier (5-5) is connected to the reducing gas manifold through a pipeline;

a feed port of the venturi cooler (6-1) is connected to a discharge port of the discharger (5-3); an inlet of the venturi cooler (6-1) is The air outlet of the cyclone cooler (6-3) is connected by a pipe; the air outlet of the venturi cooler (6-1) is connected to the air inlet of the second cyclone (6-2) through a pipe; An air outlet of the second cyclone (6-2) is connected to an air inlet of the gas heater (5-4) through a pipe; a discharge port of the second cyclone (6-2) Connected to the inlet of the cyclone cooler (6-3); the inlet of the cyclone cooler (6-3) is connected to the purge nitrogen manifold; the outlet of the cyclone cooler (6-3) Connected to the inlet of the venturi cooler (6-1) through a pipe; the discharge port of the cyclone cooler (6-3) and the inlet of the secondary cooling device (7) pass through the pipe Connected

a feed port of the secondary cooling device (7) is connected to a discharge port of the cyclone cooler (6-3) through a pipe; a discharge port of the secondary cooling device (7) and the low price The feed port of the vanadium oxide silo (8-1) is connected by a pipe; the water inlet of the secondary cooling device (7) is connected to the process water main pipe through a pipe; the water outlet of the secondary cooling device (7) is The water inlet of the water cooling system is connected by a pipe;

a discharge port at the bottom of the low-priced vanadium oxide silo (8-1) is connected to a feed port of the low-cost vanadium oxide screw feeder (8-2); the low-cost vanadium oxide spiral feed a discharge port of the device (8-2) and a feed port of the dissolution activation device (9) connected through a pipe;

The clean water inlet of the stirring and dissolving device (9-1) is connected to the clean water main pipe through a pipe; the sulfuric acid solution inlet of the stirring and dissolving device (9-1) is connected to the sulfuric acid solution main pipe through a pipe; the stirring and dissolving device ( a gas outlet of 9-1) is connected to an inlet of the exhaust gas absorption and elution tower (10) through a pipe; the stirring and dissolving device (9-1) is placed inside the microwave activation device (9-2);

a gas outlet of the exhaust gas eluting absorption tower (10) is connected to a gas inlet of the induced draft fan (11) through a pipe; a gas outlet of the induced draft fan (11) passes through a pipe and a bottom of the chimney (12) The gas inlets are connected.
A method for producing a 3.5 valent high purity vanadium electrolyte based on the system of claim 1 comprising the steps of:

The vanadium oxychloride in the vanadium pentoxide storage tank (1) and the nitrogen from the purified nitrogen main pipe are preheated by the vaporization of the vanadium oxychloride vanadium vaporizer (2-1), and then passed through the chloride spray gun (2- 3) entering the gas phase hydrolysis fluidized bed main body (2-4); the clean water and the purified air are vaporized and preheated by the clean water vaporizer (2-2), and then sent to the gas phase hydrolysis fluidized bed main body (2- 4) hydrolyzing vanadium oxychloride and maintaining fluidization of the powder material to form vanadium pentoxide powder and hydrolyzed flue gas rich in hydrogen chloride; the vanadium pentoxide powder is fluidized by the hydrolysis Bed bed discharger (2-5) discharge Into the vanadium pentoxide bin (3-1); the hydrolyzed flue gas is removed from the dust by the enlarged section of the gas phase hydrolysis fluidized bed main body (2-4), and then enters the hydrochloric acid exhaust gas absorber (2- 6) performing an absorption treatment to form a by-product of the hydrochloric acid solution, and absorbing the exhaust gas into the exhaust gas leaching absorber (10) for treatment;

The vanadium pentoxide in the vanadium pentoxide silo (3-1) sequentially enters the vanadium pentoxide screw feeder (3-2), the venturi preheater (4-1), After the first cyclone separator (4-2) and the cyclone preheater (4-3), together with the fine powder particles recovered from the bag filter (4-4), the feeder is passed through the feeder (5-1) entering the bed (5-2); the purified nitrogen is sequentially passed through the cyclone cooler (6-3), the venturi cooler (6-1), the second The cyclone separator (6-2) is preheated and mixed with the purified reducing gas from the gas purifier (5-5) to be preheated by the gas heater (5-4) to enter the bed body ( 5-2) maintaining the vanadium pentoxide powder material fluidized and reducing it to obtain a low-valent vanadium oxide powder and reducing flue gas; the low-valent vanadium oxide is passed through the bed (5- The discharge port of 2) sequentially enters the discharger (5-3) together with the fine powder recovered by the cyclone (5-6), the venturi cooler (6-1), the first After the cyclone separator (6-2), the cyclone cooler (6-3), and the secondary cooler (7) are cooled, the low-valent vanadium oxygen is introduced. In the material silo (8-1); the reduced flue gas in the bed (5-2) sequentially enters the cyclone (5-6), the cyclone preheater (4-3), Said venturi preheater (4-1), said first cyclone separator (4-2), after said dust removal by said bag filter (4-4), entering said exhaust gas leaching absorber (10), The gas discharged after the absorption treatment by the alkali solution is sent to the chimney (12) through the induced draft fan (11) and then emptied;

The low-valent vanadium oxide in the low-valent vanadium oxide silo (8-1) enters the stirring and dissolving device (9-1) through the low-valent vanadium oxide screw feeder (8-2), The microwave activating device (9-2) provides a high-purity vanadium electrolyte solution by the dissolution of the sulfuric acid solution from the clean water and the sulfuric acid solution main pipe from the clean water main pipe by the microwave field, and the generated acid mist gas is sent. The exhaust gas eluting absorber (10) is processed.
The method for producing a 3.5-valent high-purity vanadium electrolyte according to claim 2, wherein the vanadium oxychloride raw material has a purity of from 99% to 99.9999%.
The method for producing a 3.5-valent high-purity vanadium electrolyte according to claim 2, wherein in the vanadium oxychloride vaporizer (2-1), the vaporization operation temperature is 40 to 600 ° C, nitrogen gas and trichlorobenzene. The vanadium oxide molar ratio is from 0.10 to 10.00.
The method for producing a 3.5-valent high-purity vanadium electrolyte according to claim 2, wherein in the clean water vaporizer (2-2), the vaporization operation temperature is 40 to 600 ° C, and the mass ratio of air to water It is 0.10 to 10.00.
The method for producing a 3.5-valent high-purity vanadium electrolyte according to claim 2, wherein in the gas phase hydrolysis fluidized bed main body (2-4), the pentoxide is directly prepared by vapor phase hydrolysis of vanadium oxychloride In the vanadium powder, the mass ratio of water vapor to vanadium oxychloride is 0.10 to 10.00, the gas phase hydrolysis operation temperature is 100 to 600 ° C, and the average residence time of the powder is 15 to 300 min.
The method for producing a 3.5-valent high-purity vanadium electrolyte according to claim 2, wherein in the reduced fluidized bed main body (5-2), the operating temperature of the reduction is 400 to 700 ° C, and the reducing gas is as described above. After purification by the purifier (5-5), the organic matter content is less than 1 mg/Nm 3 , the total content of solid particles is less than 2 mg/Nm 3 , and the integral number of reducing gas in the mixed gas of nitrogen and reducing gas is 10% to 90%, powder The average residence time of the material is 30 to 90 minutes.
The method for producing a 3.5-valent high-purity vanadium electrolyte according to claim 2, wherein the sulfuric acid solution is a sulfuric acid solution having an electron-grade purity and a molar concentration of 4.0 to 10.0 mol/L.
The method for producing a 3.5-valent high-purity vanadium electrolyte according to claim 2, wherein the high-purity vanadium electrolyte is a mixture of V(III) and V(IV) vanadium ions in a molar ratio of 1:1. The vanadium electrolyte has an average valence of 3.5.
The method for producing a 3.5-valent high-purity vanadium electrolyte according to claim 2, wherein in the dissolution activation device (9), an external microwave field is used to assist the dissolution of the low-valent vanadium oxide and to activate the vanadium ion. The dissolution activation time is 30 to 300 minutes, the dissolution activation temperature is 20 to 45 ° C, the microwave power density is 10 to 300 W/L, and the microwave frequency is 2450 MHz or 916 MHz. .